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11.
The problem of calculating the thermodynamic properties of two-dimensional semiclassical hard-body fluids is studied. Explicit expressions are given for the first-order quantum corrections to the free energy, equation of state, and virial coefficients. The numerical results are calculated for the planar hard dumbbell fluid. Significant features are the increase in quantum corrections with increasing eta and increasing L*=L/sigma(0). 相似文献
12.
Ballester P Costa A Castilla AM Deyà PM Frontera A Gomila RM Hunter CA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(7):2196-2206
Three isomeric zinc bisporphyrins have been prepared by covalently linking together two aminoporphyrins with an isophthalic acid derivative. The porphyrins differ in the substitution pattern on the meso phenyl groups, that is, ortho, meta, or para. Titrations carried out by UV-visible and 1H NMR spectroscopy have been used to map out the stabilities and the stoichiometries of the complexes formed with 1,4-diazabicyclo[2.2.2]octane (DABCO) in chloroform. The ortho- and meta-substituted bisporphyrins form 1:1 intramolecular sandwich complexes. The para-substituted bisporphyrin cannot adopt the cofacial conformation required for this type of complex and forms a higher order 2:2 intermolecular assembly, which is stable over a wide range of DABCO concentrations. 相似文献
13.
The Conversion of Eperuic Acid into Ethers of the enantio-14, 15-Dinorlabdane Series 5 and 6 are strongly odiferous substances of the ambra-type. Their enantiomers 7 and 8 , hitherto unknown, have been synthesized from eperuic acid (4) and their olfactory properties compared with those of 5 and 6 . 4 was esterified by CH2N2 and dehydrogenated with (C6H5Se)2/H2O2 to the α,β-unsaturated ester 9 (61%). Oxidation by KMnO4 in acetone yielded the ketone 3 (60%). Epoxidation followed by treatment with acid converted 3 into the acetals 7 (61%) and 8 (14%). 7 and 8 differ from 5 and 6 in odor intensity, and 6 and 8 show slightly different odor quality. 相似文献
14.
Rate constants for the reactions of e aq ? , H and OH radicals with 2-pyridine carboxaldehyde and 2-pyridine methanol have been determined by pulse radiolysis technique. Reactions of reducing radicals such as acetone ketyl radicals and CO2 ? with these compounds were also evaluated at various pHs. The species produced by the reaction of reducing radicals with these solutes was a strong reductant itself. While pyridinyl were produced in the case of 2-pyridine methanol, one-electron reduction of 2-pyridine carboxaldehyde led to the formation of PyCHOH radical. The one-electron reduction potential of PyCHOH radicals was estimated by establishing an equilibrium with MV+ radical cations to be ?0.6V vs NHE. OH radical reaction with 2-pyridine carboxaldehyde gave an OH adduct, while in the case of 2-pyridine methanol, OH radicals reacted partly by H-abstraction from the ?CH2OH group. SO4 ? radical reaction with 2-pyridine carboxaldehyde produced a species which was reducing in nature. The rate constants for the reaction of e aq ? and OH radicals are compared with similar values obtained in the case of other 2-pyridine derivatives to see if there is any electron-inductive effect. 相似文献
15.
We present a method for computing classical Newtonian trajectories that minimize the path length or transit time from reactant
to product. Our approach is based on a generalization of the fast-marching method, which allows us to construct the solution
of the Hamilton-Jacobi equation for the action that optimizes the desired quantity. The resulting “reactive paths” can be
interpreted as reaction coordinates but, unlike more conventional choices, they contain dynamical information about the chemical
system of interest. 相似文献
16.
Gurucharan Mukherjee Sailendra Nath Poddar Kingshuk Choudhury Kamalendu Dey 《Transition Metal Chemistry》1988,13(1):58-63
Summary Iron(III) complexes of a quadridentate N2S2 donor ligand, 1,2-di(o-aminophenylthio)ethane (DAPTE) and its Schiff Base with salicylaldehyde, a hexadentate N2S2O2 donor ligand,viz. 1,2-di(o-salicylaldiminophenylthio)ethane (H2DSALPTE) have been synthesised and characterised.The Schiff base ligand (1 mol) gave a dark green tri-iron(III) [Fe3(DSALPTE)(HDSALPTE)Cl3]Cl2 complex when reacted with anhydrous iron(III) chloride (1 mol). The Mössbauer data of this complex suggest the presence of three iron sites, one of which is octahedral and the other two tetrahedral. On the other hand, Fe(ClO4)3 reacted smoothly with H2DSALPTE in ethanol to give a mononuclear pseudo-octahedral complex in which the ligand functions in a dibasic hexadentate fashion. Mössbauer data suggest the presence of a low-spin-high-spin equilibrium in the solid state. The manganese(III) and cobalt(III) complexes of the Schiff base, H2DSALPTE, are also studied for the sake of comparison with the corresponding iron(III) complex. The N2S2 ligand, however, formed a low-spin pseudo-octahedral iron(III) complex. The complexes have been characterised by elemental analysis, molar conductance values, cryomagnetic data and i.r., electronic and Mössbauer spectral data. 相似文献
17.
Summary A rigorous analysis of the effect of various concentrations (0.02–1.60M) of ammonium acetate on the distribution coefficients (K) of a number of metal ions using cation exchanger Dowex 50W-X8 (100–200 mesh NH4
+-form) has been made. On account of the low affinity of U(VI) for resin in 0.20M NH4OAc it can be separated from all other metal ions. HighK values of Sr(II), Ba(II) and Hg(II) at higher 0.50M NH4OAc are responsible for their separation from others. The abnormal column Chromatographic behaviour of Al(III) permits its separation from other metal ions including U(VI), Sr(II), Ba(II), Hg(II). A number of binary and ternary separations have been achieved. 相似文献
18.
We investigate the incidence matrix of a finite plane of ordern which admits a (C, L)-transitivityG. The elation groupG affords a generalized Hadamard matrixH=(h
ij
) of ordern and an incidence matrix for the plane is completely determined by the matrixR(H)=(R(h
ij
)), whereR(g) denotes the regular permutation matrix forgG. We prove that in the caseR(H) is symmetric thatG is an elementary abelian 2-group or elseG is a nonabelian group andn is a square. Results are obtained in the abelian case linking the roots of the incidence matrixR(H) to the roots of the complex matrix (H), a nontrivial character ofG. 相似文献
19.
Bankim C. Das I. Dey G. Biswas R. Banerjee Y. Iitaka A. Banerjee 《Journal of chemical crystallography》1993,23(6):509-512
The crystal structure of C6H16N8O2·CuCl2, a biguanide metal complex, has been determined by X-ray diffraction data using MoK radiation. The compound crystallizes in the monoclinic space groupP21/a, witha=11.074(4),b=12.061(4),c=5.312(3)Å and=102.8(1)°.The structure was solved by direct methods and refined by full-matrix least-squares to a finalR value 0.037 with 1245 unique reflections. The complex molecule is centrosymmetric, with the Cu atom (0.5,0.5,0.5) on a crystallographic center of symmetry. The complex molecule is rhombic planar with a trans configuration. 相似文献
20.